N,n&#39;&#39;-dibenzyl-n,n&#39;,n&#39;&#39;-trialkyl-dialkylene triamines



Patented Nov. 25, 1952 UNITED STATES @ATENT OFFICE N ,N"-DIBENZY L-N,N',N"-TRIALKYL- DIALKYLENE TRIAMINES No Drawing. Application June 23, 1956,-

Serial No. 170,032

12 Claims. (01. zed-570.9)

The present invention relates to N,N"-dibenzyl- N,N,N"-trialkyl-dialkylene triamines and to a process of preparing such triamines per se and in admixture with symmetrical dialkyl dibenzyl alkylene diamines and symmetrical N,N"-dibenzyl N,N,N",N' -tetraalkyl trialkylene tetramines which are particularly useful as gas fading inhibitors for dyeings on cellulose derivatives.

It is well known that many otherwise desirable dyes for cellulose derivatives suffer from the disadvantage that they are not fast to gas fumes, that is, the dyeings produced therewith become duller and change shade after exposure to such gases. While this phenomenon is not restricted to blue dyes derived from anthraquinone, it is particularly noticeable with such dyes because the gas fading effect is found to be more marked in the blue region of the spectrum. The antraqulnone blues and violets on cellulose derivatives have the characteristic of being extremely fast to light, washing, dry cleaning, and the like, and are most desirable dyes on cellulose derivatives excepting for the peculiarity they possess of changing to a pink or gray shade in the presence of coal gas.

This tendency of dyeings on cellulose derivatives to undergo fading when subjected to gas fumes has been recognized for many years, and since the advent of United States Patent 1,723,230 in 1929, many organic and inorganic bases have been proposed as inhibitors for such gas fading. While many of the compounds so suggested have attributes which recommend their use in the stated relationship, nevertheless none of the compounds have all of the attributes necessary to permit them to completely fulfill the task of im hibiting gas fading to the degree desired in commercial application. It is recognized that the ability of a compound to inhibit gas fading is proportional to the amount of the basic groups that a compound is capable on a weight basis of introducing into a cellulose derivative. For example,dimethylamine istheoretically capable of introducing more basic groups on a weight basis than more complex amines suggested as inhibitors for gas fading. Unfortunately, however, dimethylamine is too soluble in water to be completely extracted from water by cellulose derivatives.

United States Patent 2,017,119 discloses as in hibitors for gas fading various aralkylamines. However, due to the large amount of such compounds which are necessary to inhibit gas fading, and due to the only moderate fastness to washing, dry cleaning, and sublimation of such compounds, they have found little commercial use as inhibitors.

N,N-diphenyl ethylenediamine is disclosed in United States Patent 2,416,380. This compound," while permanent, has the marked peculiarity that it tends to develop a color of its own on exposure to gas fumes, as a consequence of which it changes a pastel blue dyeing to a green shade.

There are many requirements which a gas fading inhibitor must meet in order to be acceptable from a practical standpoint. These requirements are as follows: i

(1) It must prevent fading of the dyed cellulose derivatives when exposed to gas.

(2) It must be and remain colorless, i. e., introduce no color of it own whenexposed to gas. (This criterion, as noted above, is important for pastel dyeings where any color introduced by the inhibitor would effect a marked change in shade.)

(3) It must give no discoloration on prolonged exposure to sunlight. I

(4) It must be fast to dry cleaning and wet washing.

(5) It must be fast to sublimation.

(6) It must be odorless and non-toxic.

(7) It should be suitable for direct dyeing along with the dye in the dye bath. To this end it must exhaust from the dye bath by having a natural afiinity for cellulose derivatives and be capable of being suitably emulsified or' dispersed in Water to assure level dyeing.

When these factors are added up, it is no won'- der that the art has been searching so fruitlessly for so many years in order to obtain a gas fading inhibitor which will be eminently satisfactory from acommercial standpoint.

We now have discovered that products which meet all of the above requirements and the needs of the art as gas fading'inhibitors for dyeings on' cellulose esters and ethers are N ,N"-dib enzyl-' N,N' ,N' -trialkyl-dialkylene triamines per 'se', or inadmixture with symmetrical dialkyl dibenzyl alkylene diamines and symmetrical dibenzyl N,N,N",N" tetraalkyl-trialkylene tetramines.

To provide the N,N" dibenzyl N,N',N-trialkyl-dialkylene triamines and the process of pre paring the mixture of the corresponding diamines, triamines, and tetramines constitutes the purpose and object of the present invention.

The N ,N"-dibenzyl-N,N',N"-tria1kyl dialkylene triamines and the mixture of the corresponding diamines, triamines, and tetramines are not only useful as gas fading inhibitors .of dyeings on cellulose derivatives, but are also excellent fungicides, bactericides, anti-oxidants, and are useful for the preparation of spirit soluble azo dyestuffs. The mixture of the diamine, triamine, and tetramine gas fading inhibitor has the advantage over the diamine alone in that at higher concentrations in gas fading compositions (3% to 5% based on the weight of the fiber) the mixture is more effective than an equal weight of the diamine alone.

The N,N"-dibenzyl-N,N',N"-trialkyl dialkylene triamines contemplated as new and useful compounds in accordance with the present invention are characterized by the following general formula:

wherein Ar is a phenyl type radical, i. e., phenyl, alkylphenyl, e. g., tolyl, ethylphenyl, butylphenyl, and the like, halogenophenyl, e. g., chlorophenyl, bromophenyl, dichlorophenyl, dibromophenyl, etc., alkoxyphenyl, e. g., anisyl, ethoxyphenyl, propoxyphenyl, etc., carbalkoxyphenyl, e. g., carbomethoxyphenyl, carbethoxyphenyl, carbopropoxyphenyl, etc., aryloxyphenyl, e. g., phenoxyphenyl, methylphenoxyphenyl, etc., cyanophenyl, etc.; R represents an alkyl radical of not more than 6 carbon atoms, e. g., methyl, ethyl, propyl, butyl, and hexyl; R1 represents an alkylene group, i. e., any aliphatic open chain linking component, such as methylene, ethylene, trimethylene, propylene, tetramethylene, pentamethylene, 2- methyl-1,3-p10pylene, 3,3,3-trimethyl 1,2 propylene, 2,3-butylene, and the like.

The triamines characterized by the foregoing formula may be prepared as such or in admixture with symmetrical dibenzyl alkylene diamines having the formula:

and symmetrical dibenzyl tetraalkyl trialkylene tetramines having the following formula:

wherein Ar, R and R1 have the same values as above.

The N,N"-dibenzyl-N,N',N"-trialkyl dialkylene triamines characterized by the above formula are prepared by the reaction of a benzyl halide, such as bromide or chloride with trisubstituted triamines of the type:

wherein R and R1 have the values as described above.

The trisubstituted triamines are readily prepared according to the process described in United States Patent 2,279,294, which discloses examples of such triamines contemplated herein for the reaction with a benzyl halide. In general. the process involved. in said patent comprises reacting equimolar amounts of a primary aliphatic amine, an N,N-dialkyl substituted alkylene diamine, and an alkylene dihalide, such as bromide or chloride.

The trisubstituted triamines may also be prepared by reacting an alkylene dihalide with a primary aliphatic amine, making the reaction mixture strongly alkaline, separating the oily layer, drying, and fractionally distilling. If the proportion of reagents used is at an optimum, a considerable proportion of a fraction consisting of trisubstituted triamine will be collected.

The benzyl halide, i. e., bromide or chloride, which may be reacted with a trisubstituted triamine may be either substituted or unsubstituted, such as, for example, benzyl chloride, benzyl bromide, 3-methylbenzyl chloride or bromide, 3,4-di-methylbenzyl chloride or bromide, 5-chlorobenzyl chloride or bromide, o-bromobenzyl chloride or bromide, and the like.

The following are examples of suitable alkylene dihalides, i. e., the bromides and chlorides which may be reacted to yield the trisubstituted triamines, andexamples of suitable primary aliphatic amines.

AZkz Zene dihalides ethylene chloride 1,3-propylene chloride tetramethylene chloride pentamethylene chloride 1,2-propylene chloride 2,3-butylene chloride Primary aliphatic amines methylamine ethylamine N-propylamine isopropylamine N-butylamine secondary butylamine tertiary butylamine In practicing the present invention, the N,N"- dibenzyl-N,N,N-trialkyl dialkylene triamines may be prepared as follows:

Six to six and a half chemical equivalents of a primary aliphatic amine are charged into a pressure vessel; then one chemical equivalent of an alkylene dihalide is added gradually over a three hour period. After the dihalide has been added, the temperature is kept constant at about 1 0-90" C. for 2 to 3 hours. The mixture is cooled to a temperature ranging from room temperature to C. and the excess amine evaporated. Dry sodium hydroxide, or similar strong base, is added to the cooled reaction mixture and the excess primary aliphatic amine is distilled off by heating the pressure vessel to 90 C. for about 2 to 3 hours. Approximately four chemical equivalents of unreacted primary aliphatic amine may be recovered. The pressure vessel is then cooled to room temperature, opened, and a sufficient quantity of benzene or similar inert solvent added to aid in removing the slurry which contains a mixture of amines and sodium halide. The salt is filtered off and washed with benzene.

I The benzene-water filtrate containing the mixture of amines some of which are dissolved is then fractionally distilled and the benzene-water azeotrope is collected at vapor temperature of about 69 C. The benzene-water mixture collected is separated and the benzene fraction of it is added to the pressure vessel, and more benzenewater distilled off until no more water is collected. The temperature in the vapor rises to 81 C. when no more water is distilled and benzene alone is collected at this temperature.

After the benzene is fractionally distilled off, the symmetrical dialkyl-alkylene diamine is distilled off. The residue is then fractionally distilled at reduced pressure. The first fraction distilled at reduced pressure consists of the trialkyldialkylene triamine.

The trialkyl-dialkylene triamine compounds are benzylated as follows:

To a one molar solution of the triamine in benzene is added mol of a benzyl halide. The mixture is then heated at (SO-70 C. until the added benzyl halide is completely reacted. (The endpoint of this reaction may be determined by withdrawing small aliquots of the benzene solution occasionally, slurrying with water, and measuring 5 the pH.) When the pH as determined in this manner drops no further, the /2 mol of benzyl halide has reacted. After the /2 mol of benzyl halide has reacted, A; mol of aqueous caustic is added, and the mixture is stirred until the pH of 10 a withdrawn sample rises no higher (tested as described above). After this another A; mol of benzyl halide is added, and the mixture stirred until reaction is complete. It is then neutralized with aqueous caustic as described above. The same procedure is repeated until a total of 2 mols of benzyl halide and 2 mols of aqueous caustic has been added and reacted completely in the above described portionwise manner.

The benzene solution then is treated with water and the layers separated. The benzene then is distilled from the product, leaving as residue the desired dibenzyl trialkyldlalkylene triamine.

For instance, 1,2-dichloropropane and methylamine are reacted to give a mixture of compounds:

and 3o chloric acid, and (b) may be separated out as the trihydrochloride on treating the aqueous acid solution with salt. The crystalline trihydrochloride of (b) after filtering off may be converted back to the free amine by treatment with aqueous caustic soda, whereupon it forms an oily layer on top of the aqueous layer. This general technique is illustrated by Example V below.

Or again, ethylene chloride and methylamlne are reacted and the reaction mixture fractionally distilled after alkalizing and drying. The symmetrical ethylenediamine:

on, CH1

, is the first fraction collected, and the second fraction consists of N,N',N"-trimethyl-diethylene trlamine:

H onl-om-N-oizn HaC-N CHzOH -CH: which is then benzylated with benzyl chloride, and the resulting N,N"-dibenzyl-N,N',N"-trimethyl-diethylene triamine, characterized by the formula:

Ha Ha N,N ,N' ,N -tetramethyl triethylene tetramine' of the formula:

CH3 OH: CE:

of the products to give a mixture of dibenzyl amines of the type:

(a) 0113 cm Hz (b) CH3 r- CH1 CH3 CHa The mixture of amines is extracted with dilute aqueous hydrochloric acid, whereupon the compounds (b) and (c) are converted to hydrochlorides before (a). In other Words, (b) and (0) contain amino groups which are considerably more basic than are those of (a). In competing for a limited amount of acid, (b) and (c) are converted to water-soluble monohydrochlorides before (a) Thus, by extracting the total mixture with a calculated amount of dilute hydrochloric acid, it is possible to isolate (a). The aqueous mixture consisting of (b), (0), etc., is then converted to the complete hydrochlorides (i. e., all amino groups acidified) using strong hydro- This mixture may be separated from any monobenzylated amine and other products (like N,N'-dimethyl piperazine) by extraction or fractional distillation at reduced pressure. I

Although the invention is not to be limited thereby, the following examples will illustrate how the present invention may be practiced.

PREPARATION OF DIBENZYL TRIAMINES Example I 1535 grams of anhydrous methylamine is placed in a one gallon autoclave and for a three hour period there is gradually added at 70 C. 735 grams of ethylene chloride. After all the ethylene chloride has been added, the temperature is kept at 70 C. for 2 hours. The reaction mixture is cooled to 40 C. and the excess free methylamine evaporated. 600 grams of dry sodium hydroxide is added. The methylamine i 8 distilled ofi' by heating; the autoclave, to 70 C. The residue in the autoclave is distilled at and; the distillate collected in, a receiving vessel 1.0 mm- Of mercury a e fr ct on d s li is cQoled in dry. ice bath containing methanol, at 60 C. iS distilled and the residue discarded.

The distillate, which is substantially N,N,N"-v trimethyl diethylene triamine, is benzylated as in Example I. The compound obtained after the In three hours a total of 1070 grams of methylamine is collected, thus indicating that 465 grams is actually used during the condensation extraction procedure described in Example I IS reaction. The autoclave s cooled to room term (by analysis) y perature' Opened and 800 grams of benzene dieth lene triamine and is characterized b the added. The slurry is removed, the salt filtered g y oil and washed with 1000 grams of benzene.

Titration of an aliquot portion of the filtrate OCHz-N-CIIz-CHr-N-CHg-CH2NC'H2-C showed 11.5 equivalents of amine present. ([3113 Ewamplell (11H: CH: CH3

In benzylating the crude reaction product ob- 1535 grams of anhydrous methylamine are tained above, the filtrate is transferred to a placed in a 1 gallon autoclave and 840 grams of 5-liter, 4-necked flask equipped with a ther- 1,2-dichloropropane are added gradually over a mometer, stirrer, condenser, and dropping funnel. 3 hour period at 90 'C. After all the dichloro- Two-hundred and fifty grams of benzyl chloride propane has been added, the temperature are dr pped into the flask over a half hour period gradually raised to 105 C. and held at this point at. about 55 C. The mixture is stirred for 2 for 2 hours. The product then is cooled to 40 C., hours at 60 C. and then '78 grams of dry sodium the excess methylamine is evaporated off, and hydroxide pellets added. The heating is con- 600 grams of dry sodium hydroxide are added. tinued for a half hour at 60 C. and this operation The methylamine is distilled off by raising the is repeated three more times by the addition of 00 temperature in th uto mve t 70 c, a d 1- 250 grams of benzyl chloride followed by '78 lected by cooling the receiver in a Dry-Ice algrams of sodium hydroxide and the stirring concohol bath. When all the methylamine is retinued for the same length of time after e c moved, the product is cooled to room temperaaddition as in the first. Then at 55 C. a final ture and 800 grams of benzene are added. The portion of 125 grams of benzyl chloride is added lt i removed by filt ti d th lt k opwise over a half ho r per od and heating is Washed with 1 liter of benzene. The combined continued for 3 hours at 60 C. A total of 1125 filtrate and washings are distilled through a grams o b y Chloride and 312 grams of Caustic fractionating column. A mixture of water and soda is utilized in the fou p ed Operations benzene is distilled oiT at 69 C. (1 atmosphere).

The benzene is then distilled ofi from the mix- 40 After n t Water is distilled fi t t ture, and about 1700 mls. of benzene is collected ture rises to 80 C. Almost pure benzene then (which contains 0.7 equivalent Of amine). The djstills over, When the benzene is completely material in the flask is ransferred to a s p removed by distillation, the temperature rises to tory funnel and treated with 1600 mls. of water. 124 G, Then t Compound After shaking thoroughly the aqueous layer is separated oh and the top layer (organic) is CHSNHCHWHDCHZNHCPH treated with 600 mls. of water, shaken, and the fig??? sagg s g zg fga gfg g gg? phere). The residue is transferred to a vacuum m distilling system and at 26 mm. of mercury and shaken, and the water layer diawn off. The D 50-65 C. the final product is distilled. It is resulting organic layer, weighing about 1180 characterized b the formula grams, consists of a mixture containing y symmetrical dimethyl dibenzyl ethylenediamine, 30% of N,N-dibenzyl-N,N',N"-trimethyl-die 9 Y 'Q ethylene triamine, and 10% of dibenzylated 55 CH1 1 CE: O

is distilled over at this temperature (1 atmoshigher amine condensation products.

Example II which was established by chemical analysis. In preparing N,N"-dibenzyl-N,N',N-trimethyl The benzylation of the material is carried out diethylene triamine, the condensation reaction as follows:

of methylamine and ethylene chloride is run Sixteen grams of the above compound are in the same way as in Example I. As before mixed with 100 mls. of benzene and 5 mls. of the salt is filtered off, the cake washed with water in a 250 mls. round bottom flask. It is 1000 grams of benzene, and the benzene-water benzylated with a total of 30.5 grams of benzyl filtrate containing the mixture of amines is then chloride (80% of theoretical) as follows:

fractionally distilled, the water-benzene layer Seven and six-tenths grams of benzyl chlobeing collected at a vapor temperature of 70 C. ride are dripped in at 50 C. The mixture is The benzene-water mixture collected is sepastirred at C. for 4 hours. Two and threerated, the benzene added to the autoclave, and tenths grams of sodium hydroxide pellets are the benzene-water mixture distilled off until no added at 50 C. and the whole stirred for 1 hour. more water is collected. The temperature in vapor Another 7.6 grams of benzyl chloride are dripped rises to 80 C. when no more water is distilled, in at 50 C. and stirred for 3 hours at 65 C. and benzene alone is collected at this tempera- Then 2.3 grams of sodium hydroxide pellets are ture. At 116119 C., at atmospheric pressure, added and the stirring continued for 1 hour. the symmetrical dirnethyl ethylenediamine is dis- After this a third portion of 7.6 grams of benzyl tilled off. chloride is dripped in at 60 C., and the mixture other bases like lime may be used as well.

- ethylene dichloride. distilled off after treating with sodium hydroxide.

9 stirred for 3 hours at 65 0. Then 2.3 grams of sodium hydroxide pellets are added and the whole stirred for 1 hours. Finally the fourth and last portion of 7.6 grams of benzyl chloride is added and the reaction mixture is stirred for 7 hours at 70 C.

The mixture is cooled, diluted with 200 mls. of water and then is made acid to Congo paper (blue) with 25 mls. of concentrated hydrochloric acid. All the benzene is evaporated off on a steam bath, the residue is cooled, and treated with 35 mls. of 40% sodium hydroxide. The two layers are separated and the top, organic layer washed with 75 mls. of saturated salt solution. The top layer consists of the desired compound, N,N" dibenzyl-N,N,N"-trimethyldi- (1,2-propylene) -triamine.

Emample IV In the same manner as in Example III, trimethylene chloride is condensed with ethylamine to yield:

HN(OH2)s-N-(CH )iN-H 2H5 CzHs 2H6 which can be benzylated as in Example V to yield:

It is important that the benzyl chloride be added in small portions and that after each added portion has reacted, sufficient base be added to convert the amine hydrochloride to free amine. After each portion is neutralized, another fraction of benzyl chloride is added, allowed to react completely, then treatedwith base. It is not necessary that the base used be sodium hydroxide, since anhydrous sodium carbonate or possibly The small amount of water present is required to dissolve the sodium hydroxide pellets to permit neutralization of the hydrochloride formed. We

believe that this method of benzylating diamines is more successful and gives much better yields than any method of forming benzyl derivatives which we have seen reported in the literature. The success in preparing these compounds with practically no formation of quaternary ammonium chloride is only possible as a result of this technique.

Of course, in the presence of an excess of an 'acid binding agent like sodium carbonate or triethanolamine, etc., which would not react appreciably with benzyl chloride, it would also be possible to get the reaction to proceed efficiently. It is absolutely essential that the triamino dissolves in the water phase.

Example V Example III was repeated with the exception that 840 grams of 1,2-dichloropropane are replaced by a molecular equivalent amount of The excess ethylamine is The total mass is dissolved in benzene and treated with a number of equivalents of benzyl chloride equal to 80% of the number of equivalents of free amine present in the portionwise manner of Example IV. The hydrochloride formed from each portion of benzyl chloride after it has reacted with the amine is treated with sodium hydroxide and, after all the benzyl chloride has been reacted, the whole two phase system is brought to a pH of 12 and the layers separated. The benzene layer is washed with water, then treated with water and hydrochloric acid until the pH of the aqueous layer is 7. The aqueous extract of the hydrochlorides is then separated from the benzene solution. The benzene solution consists essentially of the diamine'having the following formula:

The aqueous extract of hydrochlorides is brought to a pH of 1 with concentrated hydrochloric acid and salted out with sodium chloride. The compound characterized by the following formula precipitates as the hydrochloride. It is filtered off and converted to the free base with sodium hydroxide:

Example VI Preparation of:

HN- C 2H4-N C 2H|-N-H 3H1 03H! 3H7 The above compound is prepared by the method described in Example II of United States Patent 2,279,294 by replacing the N,N-di(o-methyl cyclohexyl) ethylenediamine by a chemical equivalent amount of N,N'-di(n-propyl)ethylenediamine, replacing the o-methylcyclohexylamine by a corresponding amount of isopropyl amine and using the same amount of ethylene dibromide as in the patent. The product may be benzylated as in the preceding examples.

' ANTI-GAS FADING USE OF DIBENZYL TRIAMINES Example VII 100 parts of cellulose acetate silk fabric previously dyed with 1,4-di-(monoethylamino)- anthraquinone is placed in a bath consisting of 5000 parts of water at 50 C. containing 40 parts of a 5% aqueous solution of the condensation product of oleic acid chloride and N-methyl taurine. To this bath are added 4 parts of a mixture of the reaction product of methylamine and ethylene chloride of Example I and 20% of the condensation product of oleic acid chloride and N-methyl taurine prepared according to United States Patent 1, 932,180. The bath temperature is gradually raised to C. and

maintained for a half hour. After the dyeing is complete, the cloth is removed, rinsed and dried. The dyed cloth shows excellent resistance toward gas fading.

Example VIII Two parts of a mixture of N,N-dibenzyl- N,N,N"-trimethyl-diethylene triamine (80%) prepared according to Example 11 and a Surface active agent consisting of the condensation product of ethylene oxide with di-isobutylphenol (20%) are added to a dye bath containing 0.6

11 part of 1-methylamino-4-ethy1ainino anthraquinone and 100 parts of cellulose acetate fabric.

The temperature isgradually raised to 85 C. after which the fabric is worked for 1 hour in the bath at 85 C. After the dyeing is complete, the fabric is removed, washed and dried. The dyed cloth shows excellent resistance toward gas fading.

The above surface active addition product of ethylene oxide may be prepared according to United States Patent 2,213,477.

It is interesting to note that the corresponding triethyl compound gives much less gas fading protection.

Example IX 12 carbon atoms designated by an asterisk. This fact, however, has not been established.

Materials other than those mentioned may be used with the anti-acid faders in question, i. e.,

0 fibers or fabrics containing a cellulose ester, such as cellulose formate, cellulose propionate, cellulose butyrate, cellulose-acetate-propionate, cellulose-acetate-butyrate, or cellulose ethers, such as cellulose methyl ether, cellulose ethyl ether, cellulose benzyl ether and the like. Accordingly, we do not intend to be limited in the patentgranted except as necessitated by the appended claims di-isobutylphenol and 80% of benzylated triamine of the following formula:

CH: CH:

are added to a dye'bath containing '16'parts "of the dye, 1-hydroxyethylamino-4-ethylamino anthraquinone, and 100 parts of cellulose acetate fabric. The temperature is gradually raised to 85C. after which the fabric is worked for 1 hour inthe bath at 85 C. After dyeing the fabric is removed, washed and dried. The dyed cloth shows 'excellent resistance to gas fading.

Example XI 100 parts of cellulose acetate silk previously dyed with 1,4- di(monomethylamino)anthraquinone are placed in a bath of 5000 parts of water at 50 0., containing 40 parts of the condensation product of oleic acid chloride and N- We claim:

'1. 'NjN dibenzyl-NN,N" trialkyl-dialkylene triamine characterized by the following general formula:

R R R wherein Ar represents a pheny lradical, R represents an alkyl radical of not more than '6 carbon atoms, and R1 represents a lower alkylene radical.

2. N,N dibenzyl N,N,N-trimethyl diethylene triamine characterized by the following formula:

40 OCHr T CHr-CHz-lf-CHz-CHz-ij-CHfiO CH3 CH3 H1 3. N,N dibenzyl N,N,N triethyl diethylene triamine characterized by the following formula:

ObHZ-N-CHTCHTN-CHTCHrN-CHQ t t t 2H5 2H: 2H;

4. N,N" dibenzyl N,N'.,N" trimethyl di- 5 trimethylene triamine characterized by the following formula:

QCHr-N-CHz-CHz- CHz-N-CHz CHPCHg-bK-CHQ c t 5 methyl taurine. To this bath are added 4 parts of a mixture of of the compound:

CH3 CH3 and 20% of the condensation product of ethylene oxide with di-isobutylphenol. The bath temperature is gradually raised to C. and the temperature maintained for a period of one-half hour. After the dyeing is completed, the cloth is withdrawn from the bath, rinsed and dried. The dyed cloth shows very good resistance to gas fading.

It appears from the formula as written that the methyl groups in the above compounds located outside the brackets are attached to the 75 5. N,N" dibenzyl N,N',N" -"triethy1ditri- 5 methylene triamine characterized by the following formula:

OoHHTI- oHna-I Homen-011G C2115 CzHs CzHs 0 6. 'N,N dibenzyl N,N,'N" trimethyl dipropylene triamine characterized by the following formula:

CH: HI H: H:

7. The process for the production of N,N"- dibenzyl-polyamines which comprises reacting a lower alkylamine with a lower alkylene dihalide by gradually adding the said halide to the said amine for a three-hour period and thereafter maintaining a temperature ranging from 70-90 C. for a period of two to three hours, cooling the reaction mixture and distilling off the unreacted amine, treating the reaction mixture with caustic alkali and heating it to atemperature of 70-90 C., and distilling the remainder of the unreacted amine, cooling the treated reaction mixture and adding thereto benzene to form a slurry, filtering the alkali salt from the slurry, alkylating the crude reaction mixture with a benzyl halide at a temperature of 60-70 0., distilling ofi the benzene and treating the alkylated mixture with water to separate it into an aqueous layer and an oily layer containing the N,N"- dibenzyl polyamines.

8. The process according to claim 7, wherein the lower alkylamine is methylamine and the alkylene dihalide is ethylene chloride.

9. The process according to claim '7, wherein the lower alkylamine is methylamine and the alkylene dihalide is 1,2-dich1oropropane.

WILLIAM W. WILLIAMS. ALBERT F. STROBEL.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,272,733 Treboux et a1 Feb. 10, 1942 2,317,757 Graf Apr. 27, 1943 2,334,782 Martin Nov. 23, 1943 FOREIGN PATENTS Number Country Date 598.312 Great Britain Feb. 16, 1948 

1. N,N" - DIBENZYL-N,N'',N"-TRIALKYL-DIALKYLENE TRIAMINE CHARACTERIZED BY THE FOLLOWING GENERAL FORMULA: 